The present invention is directed to the synthesis of novel cyclooctatetraene derivatives and their use in organic light emitting devices (OLEDs) comprising an electron transporting layer (xe2x80x9cETLxe2x80x9d) comprising said derivatives of cyclooctatetraene.
Organic light emitting devices (OLEDs) are comprised of several organic layers in which one of the layers is comprised of an organic material that can be made to electroluminesce by applying a voltage across the device, C. W. Tang et al., Appl. Phys. Lett. 1987, 51, 913. Certain OLEDs have been shown to have sufficient brightness, range of color and operating lifetimes for use as a practical alternative technology to LCD-based full color flat-panel displays (S. R. Forrest, P. E. Burrows and M. E. Thompson, Laser Focus World, February 1995). Since many of the thin organic films used in such devices are transparent in the visible spectral region, they allow for the realization of a completely new type of display pixel in which red (R), green (G), and blue (B) emitting OLEDs are placed in a vertically stacked geometry to provide a simple fabrication process, a small R-G-B pixel size, and a large fill factor, International Patent Application No. PCT/US95/15790.
A transparent OLED (TOLED), which represents a significant step toward realizing high resolution, independently addressable stacked R-G-B pixels, was reported in International Patent Application No. PCT/US97/02681 in which the TOLED had greater than 71% transparency when turned off and emitted light from both top and bottom device surfaces with high efficiency (approaching 1% quantum efficiency) when the device was turned on. The TOLED used transparent indium tin oxide (ITO) as the hole-injecting electrode and a Mgxe2x80x94Ag-ITO electrode layer for electron-injection. A device was disclosed in which the ITO side of the Mgxe2x80x94Ag-ITO layer was used as a hole-injecting contact for a second, different color-emitting OLED stacked on top of the TOLED. Each layer in the stacked OLED (SOLED) was independently addressable and emitted its own characteristic color. This colored emission could be transmitted through the adjacently stacked, transparent, independently addressable, organic layer or layers, the transparent contacts and the glass substrate, thus allowing the device to emit any color that could be produced by varying the relative output of the red and blue color-emitting layers.
PCT/US95/15790 application disclosed an integrated SOLED for which both intensity and color could be independently varied and controlled with external power supplies in a color tunable display device. The PCT/US95/15790 application, thus, illustrates a principle for achieving integrated, full color pixels that provide high image resolution, which is made possible by the compact pixel size. Furthermore, relatively low cost fabrication techniques, as compared with prior art methods, may be utilized for making such devices.
II.B.1. Basics
II.B. 1.a. Singlet and Triplet Excitons
Because light is generated in organic materials from the decay of molecular excited states or excitons, understanding their properties and interactions is crucial to the design of efficient light emitting devices currently of significant interest due to their potential uses in displays, lasers, and other illumination applications. For example, if the symmetry of an exciton is different from that of the ground state, then the radiative relaxation of the exciton is disallowed and luminescence will be slow and inefficient. Because the ground state is usually anti-symmetric under exchange of spins of electrons comprising the exciton, the decay of a symmetric exciton breaks symmetry. Such excitons are known as triplets, the term reflecting the degeneracy of the state. For every three triplet excitons that are formed by electrical excitation in an OLED, only one symmetric state (or singlet) exciton is created. (M. A. Baldo, D. F. O""Brien, M. E. Thompson and S. R. Forrest, Very high-efficiency green organic light-emitting devices based on electrophosphorescence, Applied Physics Letters, 1999, 75, 4-6.) Luminescence from a symmetry-disallowed process is known as phosphorescence. Characteristically, phosphorescence may persist for up to several seconds after excitation due to the low probability of the transition. In contrast, fluorescence originates in the rapid decay of a singlet exciton. Since this process occurs between states of like symmetry, it may be very efficient.
Many organic materials exhibit fluorescence from singlet excitons. However, only a very few have been identified which are also capable of efficient room temperature phosphorescence from triplets. Thus, in most fluorescent dyes, the energy contained in the triplet states is wasted. However, if the triplet excited state is perturbed, for example, through spin-orbit coupling (typically introduced by the presence of a heavy metal atom), then efficient phosphoresence is more likely. In this case, the triplet exciton assumes some singlet character and it has a higher probability of radiative decay to the ground state. Indeed, phosphorescent dyes with these properties have demonstrated high efficiency electroluminescence.
Only a few organic materials have been identified which show efficient room temperature phosphorescence from triplets. In contrast, many fluorescent dyes are known (C. H. Chen, J. Shi, and C. W. Tang, xe2x80x9cRecent developments in molecular organic electroluminescent materials,xe2x80x9d Macromolecular Symposia, 1997, 125, 1-48; U. Brackmann, Lambdachrome Laser Dyes (Lambda Physik, Gottingen, 1997) and fluorescent efficiencies in solution approaching 100% are not uncommon. (C. H. Chen, 1997, op. cit.) Fluorescence is also not affected by triplet-triplet annihilation, which degrades phosphorescent emission at high excitation densities. (M. A. Baldo, et al., xe2x80x9cHigh efficiency phosphorescent emission from organic electroluminescent devices,xe2x80x9d Nature, 1998, 395, 151-154; M. A. Baldo, M. E. Thompson, and S. R. Forrest, xe2x80x9cAn analytic model of triplet-triplet annihilation in electrophosphorescent devices,xe2x80x9d 1999). Consequently, fluorescent materials are suited to many electroluminescent applications, particularly passive matrix displays.
II.B.1.b. Overview of invention relative to basics
This invention pertains to the use of cyclooctatetraene derivatives to enhance the performance of organic light emitting devices (xe2x80x9cOLEDsxe2x80x9d).
A great deal of work has been done to optimize OLEDs. The materials for the hole transporting layer have been extensively engineered to achieve maximum efficiency and lifetime for the devices. However, the best devices to date are still made with the same electron transporting material that was reported in the seminal paper by Tang and Van Slyke, Appl. Phys. Lett. 1987, 51, 913. which material is tris-(8-hydroxyquinoline) aluminum (xe2x80x9cAlq3xe2x80x9d). While Alq3 has a good electron mobility and gives OLEDs with long lifetimes, it is chemically unstable and hole injection into the material appears to lead to degradation of the Alq3 (H. Aziz, Z. D. Popovic, et al., Science, 283, 1900-1902 (Mar. 19, 1999)). Other materials have been explored as ETLs, but none has proven to be as effective as Alq3.
A family of cyclooctatetraenes (COTs) has been prepared and tested as electron transporting agents in OLEDs. The goal here is to replace the Alq3 ETL of conventional OLEDs with a different, better material. The COT derivatives have a high energy gap, emitting in the blue to violet region of the visible spectrum and are very thermally stable (the glass transition temperature, Tg,  greater than 150xc2x0 C.). They have low volatility, making them ideal for vacuum deposition and they form stable glassy films. They are hydrolytically stable and they are compatible with a wide range of substrates and materials. Prior to this work it was not known if these materials would transport holes or electrons in optoelectronic devices.
In one embodiment of the present invention, we present the use of dihydridocarbonyltris(triphenylphosphine)ruthenium, which has been activated by treatment with a stoichiometric amount of styrene, as a catalyst to form the tetramer of respectively diphenylbutadiyne, di-p-tolylbutadiyne, di-p-methoxyphenylbutadiyne, bis-(xcex2-naphthyl)-1,4-butadiyne, bis(3-thienyl)-1,4-butadiyne, and bis-(4-trifluoromethylphenyl)-1,4-butadiyne.
In a second embodiment of the present invention, we focus on the use of this catalyst with diphenylacetylene. Under identical conditions to the first embodiment, the product is 75% 1,2,3 triphenyl naphthalene (instead of expected octa phenyl COT; octa aryl COT are made using conventional catalysts such as Ni (A. C. Cope, H. C. Campbell, J. Am. Chem. Soc., 1951, 71, 3536); the octa (meta or ortho) tolyl COT derivative is of interest because we expect it to be a more thermally stable glass based on steric reasons.
In a third embodiment of the present invention, we note that mixtures of alkyne monomers may be used to make tetramers.
In a fourth embodiment of the present invention, we note that cyclic voltammetry of the tetramers (including H-COT and Me-COT) allows measurement of the energy of the lowest unoccupied molecular orbital (xe2x80x9cLUMOxe2x80x9d) (which gives an estimate of energy of injected electron in COT material) which allows systematic prediction of optimum devices. The reduction potential of a compound measured by cyclic voltammetry correlates with the LUMO energy of the compound; knowledge of the LUMO of a given COT derivative allows one of ordinary skill to select appropriate, optimum components for use in an OLED. [Reduction potentials herein are reported with respect to the saturated calomel electrode (SCE).]
In a fifth embodiment of this invention, we describe the use of certain COT derivatives in functioning OLEDs.
These embodiments are discussed in more detail in the examples below. However the embodiments may operate by different mechanisms. Without limiting the scope of the invention, we discuss the different mechanisms.
II.B.1.c. Dexter and Fxc3x6rster mechanisms
To understand the different embodiments of this invention it is useful to discuss the underlying mechanistic theory of energy transfer. There are two mechanisms commonly discussed for the transfer of energy to an acceptor molecule. In the first mechanism of Dexter transport (D. L. Dexter, xe2x80x9cA theory of sensitized luminescence in solids,xe2x80x9d J. Chem. Phys., 1953, 21, 836-850), the exciton may hop directly from one molecule to the next. This is a short-range process dependent on the overlap of molecular orbitals of neighboring molecules. It also preserves the symmetry of the donor and acceptor pair (E. Wigner and E. W. Wittmer, Uber die Struktur der zweiatomigen Molekelspektren nach der Quantenmechanik, Zeitschrift fur Physik, 1928, 51, 859-886; M. Klessinger and J. Michl, Excited states and photochemistry of organic molecules (VCH Publishers, New York, 1995). Thus, the energy transfer of Eq. (1) is not possible via Dexter mechanism. In the second mechanism of Fxc3x6rster transfer (T. Fxc3x6rster, Zwischenmolekulare Energiewanderung and Fluoreszenz, Annalen der Physik, 1948, 2, 55-75; T. Fxc3x6rster, Fluoreszenz organischer Verbindugen (Vandenhoek and Ruprecht, Gottinghen, 1951), the energy transfer of Eq. (1) is possible. In Fxc3x6rster transfer, similar to a transmitter and an antenna, dipoles on the donor and acceptor molecules couple and energy may be transferred. Dipoles are generated from allowed transitions in both donor and acceptor molecules. This typically restricts the Fxc3x6rster mechanism to transfers between singlet states.
Nevertheless, as long as the phosphor can emit light due to some perturbation of the state such as due to spin-orbit coupling introduced by a heavy metal atom, it may participate as the donor in Fxc3x6rster transfer. The efficiency of the process is determined by the luminescent efficiency of the phosphor (F Wilkinson, in Advances in Photochemistry (eds. W. A. Noyes, G. Hammond, and J. N. Pitts, pp. 241-268, John Wiley and Sons, New York, 1964), i.e. if a radiative transition is more probable than a non-radiative decay, then energy transfer will be efficient. Such triplet-singlet transfers were predicted by Fxc3x6rster (T. Fxc3x6rster,xe2x80x9cTransfer mechanisms of electronic excitation,xe2x80x9d Discussions of the Faraday Society, 1959, 27, 7-17) and confirmed by Ermolaev and Sveshnikova (V. L. Ermolaev and E. B. Sveshnikova, xe2x80x9cInductive-resonance transfer of energy from aromatic molecules in the triplet state,xe2x80x9d Doklady Akademii Nauk SSSR, 1963, 149, 1295-1298), who detected the energy transfer using a range of phosphorescent donors and fluorescent acceptors in rigid media at 77K or 90K. Large transfer distances are observed; for example, with triphenylamine as the donor and chrysoidine as the acceptor, the interaction range is 52xc3x85.
The remaining condition for Fxc3x6rster transfer is that the absorption spectrum should overlap the emission spectrum of the donor assuming the energy levels between the excited and ground state molecular pair are in resonance. In Example 1 of this application, we use the green phosphor fac tris(2-phenylpyridine) iridium (Ir(ppy)3; M. A. Baldo, et al., Appl. Phys. Lett., 1999, 75, 4-6) and the red fluorescent dye [2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl) ethenyl]-4H-pyran-ylidene] propane-dinitrile](xe2x80x9cDCM2xe2x80x9d; C. W. Tang, S. A. VanSlyke, and C. H. Chen, xe2x80x9cElectroluminescence of doped organic films,xe2x80x9d J. Appl. Phys., 1989, 65, 3610-3616). DCM2 absorbs in the green, and, depending on the local polarization field (V. Bulovic, et al., xe2x80x9cBright, saturated, red-to-yellow organic light-emitting devices based on polarization-induced spectral shifts,xe2x80x9d Chem. Phys. Lett., 1998, 287, 455-460), it emits at wavelengths between xcex=570 nm and xcex=650 nm.
It is possible to implement Fxc3x6rster energy transfer from a triplet state by doping a fluorescent guest into a phosphorescent host material. Unfortunately, such systems are affected by competitive energy transfer mechanisms that degrade the overall efficiency. In particular, the close proximity of the host and guest increase the likelihood of Dexter transfer between the host to the guest triplets. Once excitons reach the guest triplet state, they are effectively lost since these fluorescent dyes typically exhibit extremely inefficient phosphorescence.
To maximize the transfer of host triplets to fluorescent dye singlets, it is desirable to maximize Dexter transfer into the triplet state of the phosphor while also minimizing transfer into the triplet state of the fluorescent dye. Since the Dexter mechanism transfers energy between neighboring molecules, reducing the concentration of the fluorescent dye decreases the probability of triplet-triplet transfer to the dye. On the other hand, long range Fxc3x6rster transfer to the singlet state is unaffected. In contrast, transfer into the triplet state of the phosphor is necessary to harness host triplets, and may be improved by increasing the concentration of the phosphor.
II.B.2. Interrelation of device structure and emission
Devices whose structure is based upon the use of layers of organic optoelectronic materials generally rely on a common mechanism leading to optical emission. Typically, this mechanism is based upon the radiative recombination of a trapped charge. Specifically, OLEDs are comprised of at least two thin organic layers separating the anode and cathode of the device. The material of one of these layers is specifically chosen based on the material""s ability to transport holes, a xe2x80x9chole transporting layerxe2x80x9d (HTL), and the material of the other layer is specifically selected according to its ability to transport electrons, an xe2x80x9celectron transporting layerxe2x80x9d (ETL). With such a construction, the device can be viewed as a diode with a forward bias when the potential applied to the anode is higher than the potential applied to the cathode. Under these bias conditions, the anode injects holes (positive charge carriers) into the hole transporting layer, while the cathode injects electrons into the electron transporting layer. The portion of the luminescent medium adjacent to the anode thus forms a hole injecting and transporting zone while the portion of the luminescent medium adjacent to the cathode forms an electron injecting and transporting zone. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, a Frenkel exciton is formed. Recombination of this short-lived state may be visualized as an electron dropping from its conduction potential to a valence band, with relaxation occurring, under certain conditions, preferentially via a photoemissive mechanism. Under this view of the mechanism of operation of typical thin-layer organic devices, the electroluminescent layer comprises a luminescence zone receiving mobile charge carriers (electrons and holes) from each electrode.
As noted above, light emission from OLEDs is typically via fluorescence or phosphorescence. There are issues with the use of phosphore-cence. It has been noted that phosphorescent efficiency can decrease rapidly at high current densities. It may be that long phosphorescent lifetimes cause saturation of emissive sites, and triplet-triplet annihilation may also produce efficiency losses. Another difference between fluorescence and phosphorescence is that energy transfer of triplets from a conductive host to a luminescent guest molecule is typically slower than that of singlets; the long range dipole-dipole coupling (Fxc3x6rster transfer) which dominates energy transfer of singlets is (theoretically) forbidden for triplets by the principle of spin symmetry conservation. Thus, for triplets, energy transfer typically occurs by diffusion of excitons to neighboring molecules (Dexter transfer); significant overlap of donor and acceptor excitonic wavefunctions is critical to energy transfer. Another issue is that triplet diffusion lengths are typically long (e.g.,  greater than 1400 xc3x85) compared with typical singlet diffusion lengths of about 200 xc3x85. Thus, if phosphorescent devices are to achieve their potential, device structures need to be optimized for triplet properties. In this invention, we exploit the property of long triplet diffusion lengths to improve external quantum efficiency.
Successful utilization of phosphorescence holds enormous promise for organic electroluminescent devices. For example, an advantage of phosphorescence is that all excitons (formed by the recombination of holes and electrons in an EL), which are (in part) triplet-based in phosphorescent devices, may participate in energy transfer and luminescence in certain electroluminescent materials. In contrast, only a small percentage of excitons in fluorescent devices, which are singlet-based, result in fluorescent luminescence.
An alternative is to use phosphorescence processes to improve the efficiency of fluorescence processes. Fluorescence is in principle 75% less efficient due the three times higher number of symmetric excited states.
II.C.1. Basic heterostructures
Because one typically has at least one electron transporting layer and at least one hole transporting layer, one has layers of different materials, forming a heterostructure. The materials that produce the electroluminescent emission may be the same materials that function either as the electron transporting layer or as the hole transporting layer. Such devices in which the electron transporting layer or the hole transporting layer also functions as the emissive layer are referred to as having a single heterostructure. Alternatively, the electroluminescent material may be present in a separate emissive layer between the hole transporting layer and the electron transporting layer in what is referred to as a double heterostructure. The separate emissive layer may contain the emissive molecule doped into a host or the emissive layer may consist essentially of the emissive molecule.
That is, in addition to emissive materials that are present as the predominant component in the charge carrier layer, that is, either in the hole transporting layer or in the electron transporting layer, and that function both as the charge carrier material as well as the emissive material, the emissive material may be present in relatively low concentrations as a dopant in the charge carrier layer. Whenever a dopant is present, the predominant material in the charge carrier layer may be referred to as a host compound or as a receiving compound. Materials that are present as host and dopant are selected so as to have a high level of energy transfer from the host to the dopant material. In addition, these materials need to be capable of producing acceptable electrical properties for the OLED. Furthermore, such host and dopant materials are preferably capable of being incorporated into the OLED using materials that can be readily incorporated into the OLED by using convenient fabrication techniques, in particular, by using vacuum-deposition techniques.
II.C.2. Exciton blocking layer
One can have an exciton blocking layer in OLED devices to substantially block the diffusion of excitons, thus substantially keeping the excitons within the emission layer to enhance device efficiency. The material of blocking layer is characterized by an energy difference (xe2x80x9cband gapxe2x80x9d) between its lowest unoccupied molecular orbital (LUMO) and its highest occupied molecular orbital (HOMO) This band gap substantially prevents the diffusion of excitons through the blocking layer, yet has only a minimal effect on the turn-on voltage of a completed electroluminescent device. The band gap is thus preferably greater than the energy level of excitons produced in an emission layer, such that such excitons are not able to exist in the blocking layer. Specifically, the band gap of the blocking layer is at least as great as the difference in energy between the triplet state and the ground state of the host.
For a situation with a blocking layer between a hole-conducting host and the electron transporting layer, one seeks the following characteristics, which are listed in order of relative importance.
1. The difference in energy between the LUMO and HOMO of the blocking layer is greater than the difference in energy between the triplet and ground state singlet of the host material.
2. Triplets in the host material are not quenched by the blocking layer.
3. The ionization potential (IP) of the blocking layer is greater than the ionization potential of the host. (Meaning that holes are held in the host.)
4. The energy level of the LUMO of the blocking layer and the energy level of the LUMO of the host are sufficiently close in energy such that there is less than 50% change in the overall conductivity of the device.
5. The blocking layer is as thin as possible subject to having a thickness of the layer that is sufficient to effectively block the transport of excitons from the emissive layer into the adjacent layer.
That is, to block excitons and holes, the ionization potential of the blocking layer should be greater than that of the HTL, while the electron affinity of the blocking layer should be approximately equal to that of the ETL to allow for facile transport of electrons.
[For a situation in which the emissive (xe2x80x9cemittingxe2x80x9d) molecule is used without a hole transporting host, the above rules for selection of the blocking layer are modified by replacement of the word xe2x80x9chostxe2x80x9d by xe2x80x9cemitting molecule.xe2x80x9d]
For the complementary situation with a blocking layer between a electronconducting host and the hole-transporting layer one seeks characteristics (listed in order of importance):
1. The difference in energy between the LUMO and HOMO of the blocking layer is greater than the difference in energy between the triplet and ground state singlet of the host material.
2. Triplets in the host material are not quenched by the blocking layer.
3. The energy of the LUMO of the blocking layer is greater than the energy of the LUMO of the (electron-transporting) host. (Meaning that electrons are held in the host.)
4. The ionization potential of the blocking layer and the ionization potential of the host are such that holes are readily injected from the blocker into the host and there is less than a 50% change in the overall conductivity of the device.
5. The blocking layer is as thin as possible subject to having a thickness of the layer that is sufficient to effectively block the transport of excitons from the emissive layer into the adjacent layer.
[For a situation in which the emissive (xe2x80x9cemittingxe2x80x9d) molecule is used without an electron transporting host, the above rules for selection of the blocking layer are modified by replacement of the word xe2x80x9chostxe2x80x9d by xe2x80x9cemitting molecule.xe2x80x9d]
As to colors, it is desirable for OLEDs to be fabricated using materials that provide electroluminescent emission in a relatively narrow band centered rear selected spectral regions, which correspond to one of the three primary colors, red, green and blue so that they may be used as a colored layer in an OLED or SOLED. It is also desirable that such compounds be capable of being readily deposited as a thin layer using vacuum deposition techniques so that they may be readily incorporated into an OLED that is prepared entirely from vacuum-deposited organic materials.
U.S. Ser. No. 08/774,333, filed Dec. 23, 1996, is directed to OLEDs containing emitting compounds that produce a saturated red emission.
At the most general level, the present invention is directed to the synthesis of certain cyclooctatetraene (xe2x80x9cCOTxe2x80x9d) molecules and to the use of said COT molecules in organic light emitting devices comprising an electron transporting layer comprising derivatives of cyclooctatetraene (xe2x80x9cCOTsxe2x80x9d) and an emissive layer wherein the emissive layer comprises an emissive molecule, which molecule is adapted to luminesce when a voltage is applied across a heterostructure. The COTs represent a new class of wide gap electron transporters that are readily deposited in vacuum. They an be synthesized in good yield ( greater than 75% isolated yields) from commercially available starting materials.
This invention is to directed to a cyclooctatetraene molecule of the formula 
wherein R1 through R8 are selected from the group consisting of alkyl, aryl and alkynyl and wherein at least one member of R1 through R8 is different from the other members of R1 through wherein at least one member of R1 through R8 is different from the other members of R1 through R8.
Of the synthesis, dihydridocarbonyltris (triphenylphosphine) ruthenium which has been activated by treatment with a stoichiometric amount of styrene catalyzes the cyclotetramerization of diphenylbutadiyne to give the unsymmetrical 1,2,4,6-tetraphenyl -3,5,7,8- tetrakis (phenylethynyl) cyclooctatetraene in high yield. The reaction can also be used with substituted phenylbutadiynes to yield (phenylethynyl) cyclooctatetracnes.
In a first embodiment of the use of these cyclooctatetraenes in OLEDs, a member of the class of cyclooctatetraenes is used to form an electron transporting layer in an OLED wherein the hole transporting layer comprises the emissive molecule of the device.
In a second embodiment in OLEDs, a member of the class of cyclooctatetraenes is used to form an electron transporting layer in an OLED to enhance the emission of a molecule in the hole transporting layer.